Manufacture of alicyclic compounds



Patented May 16, 1944 MANUFACTURE or aucrcuc comronmis Lloyd M. Joshel, Hyattsvllle, Md., asslgnor to United States of America as represented by Claude R. Wickard, Secretary of Agriculture, and his successors in oflice No Drawing. Original application October 16,

1941, Serial No. 415,263. Divided and this application March 31, 1944, Serial No. 528,927

2 Claims. 260-666) (Granted under the act of March 8, 1883, as amended April 30, 1928; 370 0. G. 757) This application is made under the act of March 3, 1883, as amended by the act of April 30, 1928, and the invention herein described, if

the diene, whereby the alicyclic compound produced has, in each case, one'additional six-membered ring than the starting diene.

By means of this process a large number of alicyclic compounds can be synthesized which are not otherwise readily available, such as cyclohexene and derivatives thereof, including the alkyl, aryl, alkyloxy, carboalkoxy, and halogeno derivatives. In addition to these monocyclie compounds, various polycyclic compounds can also be formed.

More specifically, this invention comprises heating the ethylene and a 1,3-diene at an elevated pressure until an alicyclic compound is formed having one more six-membered ring than the original diene. In general, the reaction is indicated as follows:

where one or more of the pairs consisting of R1 and Ra. R: and R3, R4 and R5, and R: and R4 may be connecting bridge linkages consisting of .[iI-l.

n being an integer, and where substituents R1 and Re and substituents R1, Ra, Ra, Ra, R5, and

Be, not already included in a bridge linkage, are chosen from the group consisting of alkyl, aryl, alkyloxy, carboalkoxy, halogen, and hydrogen.

The particular temperature and pressure at which the reaction is most favorably carried out depends in each case upon the characteristics of the conjugated diene used. In most cases, a temperature in the range of to 300 C. is applicable,- although it is possible that certain conjugated dienes will react at lower temperatures and that greater yields may be obtained with other compounds at higher temperatures. The temperature used, however, in any case should not be so high asto have a destructive effect upon the final product being formed. The pressures used also depend a great deal upon the character of the diene being used. as well as the vessel in which the reaction is carried out. Generally, there is not a critical upper limit with respect to pressure and, ordinarily, pressures above about 1,000 pounds per square inch at room temperature can be used to obtain satisfactory results. s

The following examples will further illustrate the invention:

Example I Example II About 200 cubic centimeters of ethylene and 39 grams or 2,3-dimethyl-1,3-butadiene were sealed in'a rocking-type autoclave at room temperature 2 2,349,173 under a pressure of 1,175 pounds per square inch and heated to about 200 C. The pressure rose to 6,200 pounds per square inch. The autoclave was shaken for 21' hours at 190 to 200 C., during which the pressure gradually dropped until it became constant at 3,550 pounds per square inch. The system was then cooled to room temperature and the l,2=dimethylcyclohexeneformed was isolated by fractional distillation. The reaction is indicated as follows:

on, on, on, car-c CHr-C cn, l CH; CH: CH:- CHg C g Having thus described my invention, I claim:

1. The process of manufacturing cyclohexene, comprising heating ethylene and 1,3-butadiene at a temperature below about 300 C. and at a pressure above 1000 pounds per square inch until the cyclohexene is formed, and thence recovering the cyclohexene. I H v p 2. The process 0! manufacturing 1,2-dimethylcyclohexene, comprising heating ethylene and.

2,3-dimetl'rvl-L3-butadiene at a temperature below about 300 C. and at a pressure above 1000 pounds per square inch until the 1,2-dimethylcyclohexene is formed, and thence recovering the 1,2-dimethylcyclohexene.

LLOYD M. JOSHEL.

CERTIFICATE OF CORRECTION. Patent No. 2,5u9,1?5. May 16, 19M.

LLOYD M. JOSHEL. It is hereby certified that the above .numbefed patent was erroneously issued to "UNITED STATES OF AIERICA as REPRESENTED BY CLAUDE R. WICKARD, SECRETARY OF AGRICULTURE, and HIS SUCCESSQRS INDFFICE, as assignee, whereas said patent should have been issued to the inventor,'sa1d "JOSHEL"; in the grant, line 1 after" "THEPEQF'." insert the following -Provided, however that the said 1nvent1on' may be men-- ufactured and used by or for the Government for govern-' mental purposes without the payment of any royalty thereand that the and Letters Patent shouldbe read correction therein that the same may eonfbrm to the record of vthe case in the Patent Ofif ce. Signed and sealed this 15th day of August, A. D. 19%,

Leslie Frazer Seal) Aetir'xg Commissioner of Patents.' 

